Bioregulatory active ingredient combination

ABSTRACT

The present invention relates to the use of specific quaternized bioregulatory active ingredients in combination with triazole derivatives, in particular metconazole or an agriculturally utilizable salt thereof. Corresponding compositions are likewise described.

This application is a divisional of U.S. application Ser. No.10/474,458, filed Oct. 8, 2003, now U.S. Pat. No. 7,041,624 the entiredisclosure of which is herewith incorporated by reference, which wasfiled under Section 371 as the National Stage of InternationalApplication No. PCT/EP02/04119, filed Apr. 12, 2002.

The present invention relates to the use of specific quaternizedbioregulatory active ingredients in combination with triazolederivatives, in particular metconazole or an agriculturally utilizablesalt thereof. Corresponding compositions are likewise described.

Bioregulatory active ingredients which are employed in the field ofagriculture are, inter alia, quaternized compounds amongst which themost important representatives areN,N,N-trimethyl-N-β-chloroethylammonium chloride (CCC, chlorcholinechloride, chlormequat chloride, DE 12 94 734), N,N-dimethylmorpholiniumchloride (DMC, DE 16 42 215) and N,N-dimethylpiperidinium chloride (DPC,MQC, mepiquat chloride, DE 22 07 575). These active ingredients, inparticular chlormequat chloride and mepiquat chloride, are typicallyemployed in the production of cereals at comparatively high dosagerates. The application rate of these active ingredients amounts, as arule, to 0.3-1.5 kg/ha per application. The products are commerciallyavailable for example as aqueous active ingredient concentrates (forexample Cycocel® and Terpal brands (mixtures with ethephon) in the formof SL mixtures, BASF).

Triazoles are an important class of active ingredients in the pesticidefield. As ergosterol biosynthesis inhibitors, they are primarilyemployed as fungicides (see, for example, DE 195 20 935 A1). Sometriazoles are also employed as plant growth regulators. In addition,various of the triazoles which, as such, have fungicidal activity areoccasionally also described as having plant-growth regulatory properties(see, for example, EP 0 040 345 A2; EP 0 057 357 A2). Thus,paclobutrazole and uniconazole inhibit gibberellin biosynthesis and thuscell elongation and cell division.

The active ingredients from the class of the quaternized ammoniumcompounds can be employed together with other bioregulatory activecompounds. For example, EP 0 344 533 describes synergistic combinationswith growth-regulatory 3,5-dioxo-4-propionyl-cyclohexanecarboxylic acidderivatives such as prohexadione-calcium. DE 43 00 452 A1 proposes toemploy CCC together with tebuconazole or triadimefon for inhibitingplant growth. The use of uniconazole together with CCC is described inEP 287 787 A1 for regulating plant growth.

However, the activity of the abovementioned active ingredients andactive ingredient combinations is not satisfactory in specific cases. Itis an object of the present invention to influence plant growth in amore effective manner.

We have found that this object is achieved by the present invention bythe combined use of active ingredients from the class of the quaternizedammonium compounds and active ingredients from the triazole class, inparticular the triazole derivative metconazole.

The present invention therefore relates to the use of at least oneactive ingredient of the formula (I)

where R¹, R² and X have the following meanings:

-   -   R¹ is alkyl;    -   R² is alkyl, cyclopentenyl, haloalkyl; or where R¹ and R²        together are a radical —(CH₂)₅—, —(CH₂)₂—O—(CH₂)₂— or        —(CH₂)—CH═CH—(CH₂)—NH—;    -   X is an anionic group,        in combination with        metconazole, of the formula (II),

or an agriculturally utilizable salt thereofas bioregulator in plant production.

The use according to the invention of the active ingredient combinationas bioregulator has advantages over the individual active substances ina series of a variety of applications in plant production, both inagriculture and in horticulture.

An example of a bioregulatory application is influencing the elongationof the aerial part of the plant (growth-regulatory). This extends tovirtually all of the developmental stages of a plant.

Thus, for example, it is possible greatly to inhibit the vegetativegrowth of the shoot of plants, which manifests itself in particular inreduced elongation. Accordingly, the growth of the treated plants isstunted; also, the leaves are darker in colour. Advantageous forpractice conditions are a reduced intensity of the growth of grasses onverges, hedges, canal embankments and on turf such as parks, sportsgrounds and orchards, ornamental lawns and airports, so that grasscutting, which is laborious and expensive, can be reduced. Also, morecompact growth is desirable in a number of ornamental species.

Increasing the standing ability of crops which are prone to lodging,such as cereals, maize, oilseed rape and sunflowers, is also of economicinterest. The shortened and strengthened stem axis reduces or eliminatesthe danger of “lodging” (breaking) of plants under adverse weatherconditions before harvesting. Another important aspect is thegrowth-regulatory application for inhibiting elongation and formodifying the course of maturation over time in cotton. This makespossible completely automated harvesting of this crop plant. In fruittrees and other trees, pruning costs can be saved by means of growthregulation. At the same time, the ratio which is achieved betweenvegetative growth and fruit development is more advantageous. Moreover,biennial bearing of fruit trees may be avoided by means of growthregulation. Also, the growth-regulatory application may increase orinhibit lateral branching of the plants. This is of interest if, forexample in tobacco plants, the development of side shoots (lateralshoots) is to be inhibited in order to favor foliar growth.

Also, frost hardness may be increased substantially by means of growthregulation, for example in the case of winter oilseed rape. Here, thevegetative development of the young rapeseed plants after sowing andbefore onset of winter frost is slowed down despite favorable growthconditions. Elongation and the development of too lush a foliar or plantbiomass (which is therefore particularly sensitive to frost) areinhibited. Thus, the risk of frost damage of plants which tend toprematurely break down of floral inhibition and switch over to thegenerative phase is also reduced. In other crops too, for example inwinter cereals, it is advantageous for the stands to be well into thetillering phase in autumn owing to plant-regulatory treatment, but toenter the cold season without unduly lush growth. This preventsincreased sensitivity to subzero temperatures and—owing to therelatively low quantity of foliar biomass or plant biomass—attack by avariety of diseases (for example fungal disease). Moreover, inhibitingthe vegetative growth makes possible denser planting of the soil in anumber of crop plants so that higher yields based on the acreage can beachieved.

Moreover, higher yields both in terms of plant parts and in terms ofplant constituents can be achieved by means of growth regulation. Thus,it is possible for example to induce the growth of larger amounts ofbuds, flowers, leaves, fruits, seed kernels, roots and tubers, toincrease the sugar content in sugarbeet, sugarcane and citrus fruit, toincrease the protein content in cereals or soya or to stimulateincreased latex flux in rubber trees. In this context, the activeingredients may bring about increased yields by engaging in the plantmetabolism or by promoting or inhibiting the vegetative and/or thegenerative growth. Finally, plant growth regulation may also bring aboutshortened or extended developmental stages or else an acceleration ordelay in maturity of the harvested plant parts pre- or post-harvest.

Economically interesting is, for example, facilitated harvesting whichis made possible by the concentration, over time, of the dehiscence orreduced adhesion to the tree in the case of citrus fruit, olives or inother varieties and cultivars of pome fruit, stone fruit and shelledfruit. The same mechanism, that is to say the promotion of thedevelopment of abscission tissue between, on the one hand, fruit or leafportion and, on the other hand, the shoot portion of the plant, is alsoessential for a thoroughly controlled defoliation of useful plants suchas, for example, cotton.

Moreover, growth regulation may bring about a reduction in the waterconsumption of plants. This is particulary important in the case ofcropped areas which require artificial irrigation, which requires greatfinancial input, for example in arid or semi-arid zones. Owing to theplant-regulatory application, the irrigation intensity may be reducedand farm economics improved. The effect of growth regulators may bringabout better exploitation of the available water since, for example, thedegree of stomatal opening is reduced, a thicker epidermis and cuticulaare formed, root penetration into the soil is improved, the transpiringleaf surface area is reduced, or the microplant climate in the cropstand is advantageously affected by more compact growth.

The use according to the invention is particularly important forornamentals, especially for fruit trees, and in particular for oilseedrape.

A particular subject matter of the present invention is the use of atleast one active ingredient of the formula (I) in combination with atleast one bioregulatory active ingredient from the triazole class asbioregulator for improving root growth. The purpose of this use ispredominantly the development of an increased number of root branches,longer roots and/or an increased root surface area. This improves thewater and nutrient uptake capacity of the plants. This is advantageousin particular in the case of light, for example sandy, soils and/or whenthere is a lack of precipitation. In autumn, a larger storage root isformed in particular in winter oilseed rape to allow for more intensenew growth in spring. In spring, the improved root system providesbetter anchorage of the shoot in the ground so that the plants' standingability is markedly improved. In other plants, the storage rootconstitutes all or the major part of the plant organ to be harvested(for example other Brassicaceae such as radish, but also sugarbeet,carrots or chicory).

Improved root growth is particularly advantageous when this isaccompanied by a reduction of the vegetative growth, that is to say inparticular with reduced shoot elongation (shortening) and/or reductionof the foliar biomass or plant biomass. Accordingly, the present use isadvantageously directed at a reduction of the quotient of shoot biomassto root biomass.

This use, which is directed at the root development, takes place inparticular in cereal production, for example for wheat, barley, oats andrye, also maize and rice, and very particularly in the case of plantswhich develop storage roots, such as Brassicacea, for example radish,predominantly oilseed rape and in particular winter oilseed rape, andsugarbeet, carrots or chicory. Oilseed rape production must be mentionedin particular in this context; this is where an improved root growth isparticularly effective. In practice, this application, which is directedat the development of roots, may gain particular importance underspecific circumstances, for example in the case of relatively dry soilsand/or during the phase in which the plant develops the root system.With a simultaneous reduction of the shoot elongation, the improved rootgrowth is particularly advantageous.

The invention thus relates to the use of bioregulatory active ingredientcombinations. The use according to the invention is a combinedapplication, i.e. the use of at least one active ingredient of theformula (I)—hereinbelow referred to as “active ingredient component (a)”for the sake of simplicity—and the use of triazole derivatives, inparticular metconazole, of the formula (II), or an agriculturallyutilizable salt thereof—hereinbelow referred to as “active ingredientcomponent (b)” for the sake of simplicity—is effected in a context tosuit the intended purpose, in particular with regard to optimumefficacy. Thus, the active ingredient components (a) and (b) may inprinciple be applied jointly in one formulation (ready-to-useformulation) or separately in at least two independent formulations. Theapplication of separate formulations comprises not only the simultaneousapplication, i.e. the application at essentially the same points in timeor immediately in succession, but also the staggered application, i.e.application at different points in time. As a rule, simultaneousapplication is preferred.

Particular active ingredients of the formula (I) result when alkyl ismethyl, ethyl, isopropyl. The 2-chloroethyl group is the preferredhaloalkyl group. If the substituents together with the nitrogen atom towhich they are bonded form a cyclic radical, R¹ and R² are preferably amorpholino or piperidino group. X⁻ is, for example, a halide such asbromide and preferably chloride; sulfate; an alkyl sulfate such asmethyl sulfate; an alkylsulfonate, such as methylsulfonate; a boratesuch as pentaborate; or another anionic group which is utilizable inagriculture. In principle, divalent anionic groups are also suitable;these are employed in corresponding stoichiometric amounts relative tothe ammonium cation.

In particular borates, X⁻ is an anion of the formula (III)1/m·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w(H₂O)   (III)where

-   M is a cation of an agriculturally utilizable metal, hydrogen or    ammonium;-   B is boron;-   O is oxygen;-   A is a chelating or complexing group which is associated with at    least one boron atom or an agriculturally utilizable cation;-   x corresponds to a number of from 0 to 10;-   y corresponds to a number of from 1 to 48;-   v corresponds to a number of from 0 to 24;-   z corresponds to a number of from 0 to 48;-   m corresponds to an integer of from 1 to 6;-   w corresponds to a number of from 0 to 24.

Preferred borates of the formula (III) are those where

-   x is zero; or-   M is sodium, potassium, magnesium, calcium, zinc, manganese, copper,    hydrogen or ammonium; and/or-   y corresponds to a number of from 2 to 20, 2 to 10 or 3 to 10;    and/or-   m is 1 or 2; and/or-   w corresponds to a number of from 0 to 24.

Especially preferred borates of the formula (III) are those where

-   y corresponds to a number of from 3 to 7, in particular 3 to 5;-   z corresponds to a number of from 6 to 10, in particular 6 to 8;-   v is zero;-   w corresponds to a number of from 2 to 10, in particular 2 to 8.

Very especially preferred borates of the formula (III) are those wherey=5; z=8; v=0; m=1; w=2 to 3 (pentaborates).

If present, chelating and complexing groups A are preferably selectedfrom among hydroxycarboxylic acids, carboxylic acids, alcohols, glycols,aminoalcohols, sugars and the like compounds.

Moreover, the borates may contain water, for example in the form ofwater of crystallization in free or coordinated form or as bound waterin the form of hydroxyl groups which are bound to the boron.

Further embodiments and also the preparation of borates according to theinvention, which is known per se, are described in PCT/EP98/05149.

The active ingredient of the formula I is preferably selected from among

-   -   (a1) N,N,N-trimethyl-N-β-chloroethylammonium salts of the        formula (Ia),

(a2) N,N-dimethylpiperidinium salts of the formula (Ib) and

(a3) N,N-dimethylmorpholinium salts of the formula (Ic)

where X⁻ is in particular Cl⁻ or1/m·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w(H₂O) with the abovementionedmeanings.

Especially preferred are the active ingredient components (a1) and/or(a2), in particular N,N,N-trimethyl-N-β-chloroethyl-ammonium chloride(CCC) or the corresponding pentaborate, or N,N-dimethylpiperidiniumchloride (MQC) or the corresponding pentaborate.

In one embodiment of the present invention, the active ingredientcomponent (a) consists essentially of a compound of the formula (Ia) or(Ib) or a mixture of these.

The active ingredients from the triazole class which have suitablebioregulatory activity include in particular (b1) metconazole, (b2)triadimenol, (b3) triadimefon, (b4) cyproconazole, (b5) tebuconazole,(b6) uniconazoles, (b7) paclobutrazole and (b8) ipconazole. Those whichare preferably used, mainly with regard to improvement of root growth inaccordance with the invention, are (b1), (b5) and/or (b8).

Preferred in accordance with the invention is the use of (b1)metconazole, of the formula (II),

or of an agriculturally utilizable salt thereof.

The representation of metconazole of the formula (II) which has beenchosen here includes isomeric forms of these compounds. Those which mustbe mentioned in particular are stereoisomers, such as enantiomers ordiastereoisomers of the formulae (IIa-d). Besides the essentially pureisomers, the compounds of the formulae (II) also include their isomermixtures, for example stereoisomer mixtures. A high proportion of cisisomers is preferred, advantageously with a cis:trans ratio of 5:1 to20:1.

In the present case, the agriculturally utilizable metconazole salts arepreferably acid addition salts.

Anions of useful acid addition salts are predominantly chloride,bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate,hydrogen phosphate, phosphate, nitrate, hexafluorosilicate,hexafluorophosphate.

In one embodiment of the present invention, the active ingredientcomponent (b) essentially consists of (b1), i.e. of a compound of theformula (II). In accordance with a further embodiment, the activeingredient component (b) essentially consists of a compound selectedamong (b1) to (b8), or a mixture of these.

In a particular embodiment, N,N,N-trimethyl-N-β-chloroethyl-ammoniumchloride of the formula (Ia) or N,N-dimethyl-piperidinium chloride ofthe formula (Ib) is used in combination with metconazole, of theformulae (II).

In addition to the active ingredient components (a) and (b), the useaccording to the invention may involve further active ingredients. Theseactive ingredients may in particular take the form of those whoseactivity resembles the activity mediated by the active ingredients ofthe formula (I) or active ingredients from the triazole class, or whichcomplements this activity. Thus, it may be advantageous additionally tothe combination according to the invention to employ furtherbioregulators, in particular ethephon, prohexadione-calcium ortrinexapac-ethyl, but also herbicides, in particular imazaquin, andfungicides. Vitamins, cofactors, trace elements, in particular B, Cu,Co, Fe, Mn, Mo and Zn, minerals, amino acids and other essentialnutrients may also be expedient.

The application rates of individual active ingredients which arerequired per se for bioregulation purposes can advantageously be reducedwithin the context of the combined application according to theinvention. Thus, the application rate of active ingredients of theformula (I) can be set at less than 500 g and preferably less than 350 gper ha and the application rate of metconazole, of the formula (II), orof agriculturally utilizable salts thereof at less than 100 g andpreferably less than 50 g and in particular less than 30 g per ha.

In context with the treatment, the use according to the invention of theactive ingredients which have been described includes a method. In thismethod, an effective amount of active ingredient component (a) and aneffective amount of active ingredient component (b), as a ruleformulated to meet the requirements of agricultural practice, is appliedto the area under cultivation to be treated. The active ingredientcomponents are preferably fed to the plant as a foliar spray.

For application purposes, the active ingredient components according tothe invention may be formulated in the manner known per se, for exampleas liquid formulations such as emulsifiable concentrates (EC),suspoemulsions (SE), oil-in-water emulsions (EW), water-in-oil emulsions(EO), aqueous suspension concentrates and oil suspension concentrates(SC), microemulsions (ME), water-soluble concentrates (SL), and solidformulations such as water-dispersible powders (WP), water-dispersiblegranules (WG), water-soluble powders (SP), water-soluble granules (SG)and the like. Liquid/aqueous systems are preferred. If the activeingredients of the formula (I) are used in the form of theabove-described boron salts, solid formulations are also advantageous.

In most cases, the compositions are formulated in such a manner thatthey need to be prepared in a suitable manner prior to use by the user,which is, as a rule, the farmer, in a manner known per se. For example,it may be necessary to dilute a suitable active ingredient concentratewith water to give the desired concentration or to process it with waterto give a ready-to-use spray mixture.

Sprayable mixtures normally comprise 0.0001 to 10% by weight, preferably0.001 to 5% by weight, and in particular 0.002 to 2.0% by weight, ofactive ingredient component (a) and/or (b). To prepare a customary spraymixture, for example 0.2 to 5.0 l, preferably 0.3 to 3.0 l and inparticular 0.35 to 2.0 l of an active ingredient concentrate comprisingcomponent (a) and/or (b) may be diluted with water down to 10 to 2 000l, preferably 50 to 500 l and in particular 100 to 1 000 l. Ifappropriate, 0.1% by weight to 5% by weight (based on the spray mixture)of further anionic, cationic or nonionic surfactants, adjuvants,polymers and/or further active ingredients are added to the spraymixture. Examples of substances for such surfactants and furtheradjuvants are described hereinbelow. Those which must be mentioned inparticular are starch and starch derivatives, for example a carboxyl andsulfonyl-containing starch (Nu-Film from Union Carbide Corp.) andspreaders and extenders, such as Vapor Guard from Miller Chemical &Fertilizer Corp.

The compositions can be applied in the manner known per se, for exampleby spraying the spray mixtures with a mobile sprayer, using nozzles withultrafine distribution. The apparatuses and procedures customary forthis purpose are known to the skilled worker.

The invention thereore also relates to compositions and to thepreparation of compositions for the treatment of plants.

Accordingly, the present invention furthermore relates to compositionscomprising

-   (a) at least one active ingredient of the formula (I)

where R¹, R² and X have the abovementioned meanings; and

-   (b) metconazole, of the formula (II),

or an agriculturally utilizable salt thereof.

A particular embodiment of this subject matter are compositions withhigh active ingredient concentrations (concentrates). In this case,component (a) may amount to more than 5% by weight, preferably more than10% by weight and in particular more than 20% by weight of the totalweight of the composition. On the other hand, as a rule, it isadvantageous for component (a) to amount to less than 50% by weight,preferably less than 40% by weight and in particular less than 35% byweight of the total weight of the composition. In the case ofconcentrates, component (b) may amount to more than 0.5% by weight,preferably more than 1% by weight and in particular more than 2% byweight of the total weight of the composition. On the other hand, as arule, it is advantageous for component (b) to amount to less than 20% byweight, preferably less than 10% by weight and in particular less than5% by weight of the total weight of the composition.

The relative active ingredient contents in combination products and alsowhen applied separately vary within a wide range. According to oneaspect, relatively higher amounts by weight of active ingredientcomponent (a) than active ingredient component (b) are employed. Thisweight ratio of (a) to (b) is typically within a range of from 5:1 to30:1, preferably 7:1 to 25:1 and in particular 10:1 to 20:1. Thisapplies in particular to the use of metconazole.

In a particular embodiment, compositions according to the inventioncomprise at least one further plant active ingredient, for example,herbicides, fungicides, bioregulators, as component (c).

In the case of concentrates, the active ingredient content as the totalof components (a), (b) and (c) as a rule amounts to more than 20% byweight, preferably more than 25% by weight and in particular more than30% by weight of the total weight of the composition. On the other hand,the active ingredient content as the total of components (a), (b) and(c) as a rule amounts to less than 70% by weight, preferably less than60% by weight and in particular less than 50% by weight of the totalweight of the composition.

If appropriate, the compositions comprise a further bioregulator, inparticular ethephon, prohexadione-calcium, or trinexapac-ethyl, ascomponent (c1).

If present, component (c1) amounts as a rule to 1 to 40% by weight ofthe total weight of the composition.

In a particular embodiment of the present invention, the compositionscomprise not only the active ingredient components (a) and (b), but alsothe active ingredient component (c1), in particular chlormequat chlorideand/or mepiquat chloride and/or the corresponding borates of theformulae (Ia) or (Ib) and metconazole, of the formula (II), togetherwith ethephon and advantageously with trinexapac-ethyl.

In a particular embodiment of the present invention, the compositionscomprise at least one surfactant as surface-active component (d). Inthis context, the term “surfactant” refers to boundary-active orsurface-active agents.

Depending on the type of formulation, component (d) acts predominantlyas dispersing agent or emulsifier. Moreover, at least parts of component(d) may act as wetter.

Substances which may be used in principle are nonionic, anionic,cationic and amphoteric surfactants, the hydrophobic group includingpolymer surfactants and surfactants containing hetero atoms.

If present, component (d) amounts as a rule to 5 to 60% by weight,preferably 10 to 50% by weight and in particular 20 to 40% by weight ofthe total weight of the composition.

In a particular embodiment of the present invention, the compositionscomprise at least one further adjuvant as component (e).

Component (e) may have a variety of purposes. Suitable adjuvants areusually selected by the skilled worker to meet the requirements.

For example, further adjuvants are selected from among

-   -   (e1) minerals and trace elements which can be utilized by the        plant;    -   (e2) further solvents or diluents;

The minerals and trace elements which can be utilized by plants includein particular inorganic ammonium salts such as ammonium sulfate,ammonium nitrate, ammonium chloride, ammonium phosphate, or furtherminerals or trace elements which can be utilized by plants, inparticular ammonium nitrate fertilizer granules and/or urea. They may beintroduced into the compositions according to the invention for examplein the form of aqueous concentrates, if appropriate concentrate blends,such as, for example, Ensol solutions.

If present, component (e1) as a rule amounts to up to 40% by weight,preferably up to 30% by weight and in particular up to 20% by weight ofthe total weight of the composition.

As a rule, the compositions according to the invention comprise water.The water acts predominantly as a solvent for the active ingredientcomponent (a). As a rule, it is expedient for the water to amount toapproximately 30 to 70% by weight of the weight of component (a).

Besides water, the compositions may comprise further solvents forsoluble constituents or diluents for insoluble constituents of thecomposition. In particular metconazole, which per se is only sparinglysoluble in water, can be incorporated homogeneously into the formulationin this manner.

Substances which can be used in principle are, for example, mineraloils, synthetic oils and vegetable and animal oils, or elselow-molecular-weight hydrophilic solvents such as alcohols, ethers,ketones and the like.

If present, the above-described further solvents or diluents as a ruleamount to less than 30% by weight, preferably less than 20% by weightand in particular less than 15% by weight of the total weight of thecomposition.

Further additions which may be useful are found for example amongmineral salt solutions, which are employed for alleviating nutritionaldeficiencies and trace element deficiencies, nonphytotoxic oils and oilconcentrates, antidrift reagents, antifoams, in particular those of thesilicone type, for example Silicon SL, which is commercially availablefrom Wacker, and the like.

In a particular embodiment, the present invention relates to aqueouscompositions comprising

-   -   (a) 10 to 70% by weight of at least one active substance        selected from among (a1)        N,N,N-trimethyl-N-β-chloro-ethylammonium chloride, of the        formula (Ia), and (a2) N,N-dimethylpiperidinium chloride of the        formula (Ib) or the corresponding borates;    -   (b) 0.5 to 20% by weight, preferably 1 to 10% by weight and in        particular 2 to 5% by weight of at least one active ingredient        of the triazole class and in particular metconazole, of the        formula (II), or of an agriculturally useful salt thereof.

For the purposes of the present description, quantites are generallybased on the total weight of the composition, unless otherwisespecified. In accordance with the invention, the term “essentially” as arule refers to a percentage ratio of at least 90%, preferably of atleast 95% and in particular of at least 98%.

Compositions according to the invention can be prepared in a mannerknown per se. To this end, at least some components are combined. Itmust be taken into consideration that products, in particularcommercially available products, whose constituents may contribute tovarious components may be used. For example, a specific surfactant maybe dissolved in an aprotic solvent so that this product may contributeto a variety of components. Furthermore, small amounts of substanceswhich are undesired per se may be introduced with commercially availableproducts.

For example, the active ingredients may be mixed with the additives assolds or in the form of aqueous highly concentrated products.Preferably, for example aqueous active ingredient solutions of thequaternized active ingredients of the formula I are initially introducedat a concentration of from 50 to 80% by weight and the additives arethen incorporated with stirring. The mixture may subsequently be treatedwith a concentrate of triazole active ingredients, in particular ametconazole concentrate, in a suitable solvent.

Mixing may be effected in a manner known per se, for example byhomogenizing using suitable devices such as KPG stirrers or magneticstirrers, or the corresponding large-scale stirrers.

Within the scope of the present invention, terms such as alkyl, alkoxyand the like encompass straight-chain or branched hydrocarbon groupssuch as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl,n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl,n-tridecyl, iso-tridecyl, stearyl, n-eicosyl, preferably—unlessotherwise specified—with 1 to 8, in particular 1 to 6 and especiallypreferably 1 to 4 carbon atoms.

The term “halogen” preferably represents fluorine, chlorine, bromine andiodine, in particular fluorine and especially chlorine.

The invention is illustrated in greater detail by the examples whichfollow:

PREPARATION EXAMPLES Reference Example 1 Formulations

The tank mixes employed in Example 1 are prepared by stirring anemulsion concentrate comprising 90 g/l metconazole, of the formula (II),and an aqueous concentrate comprising 600 g/l mepiquat chloride (MQC)using a magnetic stirrer.

The formulations employed in Example 2 are prepared by introducing anemulsion concentrate comprising 60 g/l metconazole, of the formula (II),and/or an aqueous concentrate comprising 460 g/l mepiquat chloride insuitable amounts. The combination of mepiquat chloride and metconazoleis employed in the form of an aqueous SL readymix comprising 21 g/lmetconazole, 300 g/l mepiquat chloride and 610 g/l further formulationauxiliaries.

Examples 1 Biological Activity (Shoot Elongation)

Winter oilseed rape (cv. Pronto) was sown in autumn (Sep. 13, 2000) andtreated approximately one month later (Oct. 19, 2000) in accordance withthe information given in Table 1. A few weeks later, the shootelongation and the root development were assessed (A1 on Oct. 26, 2000and A2 on Nov. 16, 2000). The results of the elongation are compiled inTable 1.

TABLE 1 Shoot elongation in winter oilseed rape (rating A1 and A2)Active Stage A1: Reduction Stage A2: Reduction ingredient [g/ha] rel.length [%] rel. length [%] MQC 400 100 0 96 4 Metconazole  21 81 19 6139 MQC + 400 + 21 75 25 54 46 metconazole

The expected reduction, which was calculated using Colbi's formula, was19% for rating A1 and 41.4% for rating A2. The reductions found for theactive ingredient combination according to the invention were 25% and46%, respectively, and confirm the synergism.

Examples 2 Biological Activity (Root Growth)

Winter oilseed rape (cv. Pronto) was sown in autumn (Sep. 13, 2000) andtreated approximately one month later (Oct. 19, 2000) in accordance withthe information given in Table 2. Some of the plants were harvested inautumn on Dec. 07, 2000, while others were harvested in spring on Apr.03, 2001 and the following morphological parameters were analyzed: plantlength; shoot fresh and dry weight (drying: 24 h at 105° C.); total areaof all leaves; SPAP (relative units of green coloration determined usinga Minolta chlorophyll-measuring meter SPAP 502); root fresh and dryweight (drying: 24 h at 105° C.); storage root fresh weight; length,surface area and volume of the hair roots, and number of root tips(scanning and WinRhizo determination). The results, each of which isbased on the untreated control, are compiled in Table 2, the values forthe plants harvested in autumn being shown first and the values for theplants harvested in spring being shown second.

TABLE 2 Root growth in winter oilseed rape Storage Total root Total rootfresh root dry fresh Root hair Active weight weight weight lengthingredient [g/ha] [%] [%] [%] [%] Control — 100; 100 100; 100 100; 100100; 100 MQC 400  123; 112 120; 107 118; 94  112; 123 Metconazole 28 92; 115  94; 128  94; 115 107; 126 Metconazole 84  78; 150  75; 161 74; 138  94; 129 MQC + 400 + 28 128; 141 123; 146 111; 137 145; 130metconazole (readymix) Hair root Hair root Number of Plant Activesurface volume root tips height ingredient [g/ha] area [%] [%] [%] [%]Control — 100; 100 100; 100 100; 100 100; 100 MQC 400  131; 136 154; 157 94:123 96; 93 Metconazole 28 116; 134 125; 145  93; 112 61; 91Metconazole 84  97; 148 101; 183  87; 116 46; 86 MQC + 400 + 28 164; 144186; 173 122; 123 36; 83 metconazole (readymix) Shoot fresh Shoot dryLeaf Active weight weight surface ingredient [g/ha] [%] [%] area [%]SPAD Control — 100; 100 100; 100 100; 100 100; 100 MQC 400  111; 114112; 99  116; 103 102; 102 Metconazole 28  82; 122  85; 112  84; 106107; 103 Metconazole 84  57; 150  67; 136  61; 127 116; 104 MQC + 400 +28  83; 113  85; 101  81; 108 119; 108 metconazole (readymix)

When the treatment was carried out with the active ingredientcombination according to the invention, an increased number ofindividual roots, longer roots and/or an increased root surface areawere observed in comparison with the individual active ingredients. Inparticular, it emerged that the treatment in accordance with theinvention leads a shoot biomass/root biomass ratio which is comparablymore favorable for overwintering and for vigorous regrowth of the plantin spring.

1. A method for improving root growth in Brassicacea sugar beet, carrotor chicory production which comprises applying an effective amount of amixture comprising at least one active ingredient of the formula (I)

where R¹ and R² together are a radical —(CH₂)₅—; and X is an anionicgroup, in combination with a bioregulatory active ingredient from thetriazole class selected from the group consisting of metconazole,tebuconazole and agriculturally utilizable salts thereof.
 2. The methodof claim 1, wherein the improvement of root growth is manifested in anincreased number of root branches, in longer roots and/or in anincreased root surface area.
 3. The method of claim 1, wherein theBrassicacea production is the production of oilseed rape.
 4. The methodof claim 1 in which the active ingrendient(s) of the formula (I) areapplied in amounts of less than 500 g per ha.
 5. The method of claim 1in which the bioregulatory active ingredient from the triazole class orthe salt thereof is applied in amounts of less than 100 g per ha.
 6. Themethod of claim 1 in which the active ingrendient(s) of the formula (I)are applied in amounts of less than 350 g per ha.
 7. The method of claim1 in which the bioregulatory active ingredient from the triazole classor the salt thereof is applied in amounts of less than 50 g per ha. 8.The method as claimed in claim 1, wherein the bioregulatory activeingredient from the triazole class or the agriculturally utilizable saltthereof is tebuconazole, or the agriculturally utilizable salt thereof.9. The method of claim 8, wherein the active ingredient of the formula(I) is an N,N-dimethylpiperidinium salt of the formula (Ib)

where X⁻ is Cl⁻ or 1/m ·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w (H₂O), where Mis a cation of an agriculturally utilizable metal, hydrogen or ammonium;B is boron; O is oxygen; A is a chelating or complexing group which isassociated with at least one boron atom or an agriculturally utilizablecation; x corresponds to a number of from 0 to 10; y corresponds to anumber of from 1 to 48; v corresponds to a number of from 0 to 24; zcorresponds to a number of from 0 to 48; m corresponds to an integer offrom 1 to 6; and w corresponds to a number of from 0 to
 24. 10. Themethod of claim 9 in which N,N-dimethylpiperidinum chloride of theformula (Ib) is applied in combination with tebuconazole.
 11. The methodof claim 9 in which an N,N-dimethylpiperidinium salt of the formula(Ib), where X⁻ is [M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w (H₂O), where x=zero,y=5, z=8, v=zero, m=1 and w=2 to 3, is applied in combination withtebuconazole.
 12. The method as claimed in claim 1, wherein the activeingredient of the formula (I) is an N,N-dimethylpiperidinium salt of theformula (Ib)

where X⁻ is Cl⁻ or 1/m·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w (H₂O), where M isa cation of an agriculturally utilizable metal, hydrogen or ammonium; Bis boron; O is oxygen; A is a chelating or complexing group which isassociated with at least one boron atom or an agriculturally utilizablecation; x corresponds to a number of from 0 to 10; y corresponds to anumber of from 1 to 48; v corresponds to a number of from 0 to 24; zcorresponds to a number of from 0 to 48; m corresponds to an integer offrom 1 to 6; and w corresponds to a number of from 0 to
 24. 13. Themethod of claim 12 in which X⁻ is C⁻ or1/m·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w (H₂O), where x=zero, y=5, z=8,v=zero, m=1 and w=2 to
 3. 14. The method as claimed in claim 1, whereinthe application of the mixture is achieved by combining the activeingredient of the formula (I) and the active ingredient from thetriazole class in one application formulation and then applying theformulation, or by providing two separate application formulations, thefirst formulation comprising the active ingredient of the formula (I)and the second formulation comprising the active ingredient from thetriazole class, and applying the first formulation and the secondformulation separately either simultaneously or in succession andthereby forming the effective amount of the mixture of the activeingredient of the formula (I) and the active ingredient from thetriazole class.
 15. The method of claim 1, wherein the Brassicaceaproduction is the production of radish or oilseed rape.
 16. The methodof claim 1 wherein the bioregulatory active ingredient from the triazoleclass is metconazole, of the formula (II)

or an agriculturally utilizable salt thereof.
 17. The method of claim16, wherein the active ingredient of the formula (I) is anN,N-dimethylpiperidinium salt of the formula (Ib)

where X⁻ is Cl^(—) or 1/m·[M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w (H₂O), where Mis a cation of an agriculturally utilizable metal, hydrogen or ammonium;B is boron; O is oxygen; A is a chelating or complexing group which isassociated with at least one boron atom or an agriculturally utilizablecation; x corresponds to a number of from 0 to 10; y corresponds to anumber of from 1 to 48; v corresponds to a number of from 0 to 24; zcorresponds to a number of from 0 to 48; m corresponds to an integer offrom 1 to 6; and w corresponds to a number of from 0 to
 24. 18. Themethod of claim 7 in which N,N-dimethyl-piperidinum chloride of theformula (Ib) is applied in combination with metconazole, of the formula(II).
 19. The method of claim 17 in which an N,N-dimethylpiperidiniumsalt of the formula (Ib), where X⁻ is [M_(x)B_(y)O_(z)(A)_(v)]^(m−)·w(H₂O), where x=zero, y=5, z=8, v=zero, m=1 and w=2 to 3, is applied incombination with metconazole, of the formula (II).